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Speaker: Dr. Sameernandan Upadhyayula
Weizmann Institute of Science
(Incoming postdoc fellow at EPFL - Lausanne)
Title: "New Semiclassical Methods for Rate Constants of
Chemical Reactions".
Day and Date: Friday, August 08, 2025
Time: 11.30 am.
Venue: Room no. 350, Chemistry Department
Second floor, Annex
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Hosted by Prof. Rahul Maitra
Abstract The semiclassical instanton estimate of the thermal transmission probability for
barrier crossing reactions as derived by the WKB approximation has a well-known
deficiency. It diverges at the crossover temperature, between below the barrier and
above the barrier pathways. A solution to this problem has been presented by using
the uniform semiclassical energy dependent transmission coefficient as derived by
Kemble instead of the primitive semiclassical form .The resulting thermal
transmission coefficient does not diverge at any crossover temperature and the
crossover temperature between tunneling and thermal activation is doubled.
However, there remains a difficulty with the uniform semiclassical result of Kemble.
It predicts that the half-point, defined as the energy at which the energy dependent
transmission probability equals 0.5 occurs always when the energy equals the barrier
height, which is incorrect as exemplified for an Eckart barrier. This may be corrected
by modifying the Kemble form, either by shifting the energy or by adding a constant
term to the Euclidean action, such that the resulting thermal transmission coefficient
gives the correct leading order term upto the fourth power of the reduced Planck’s
constant, as derived by Pollak and Cao. Shifting the energy is equivalent to a
modified vibrational perturbation theory (mVPT2 and mSVPT4). Shifting the action
by a constant generalizes a correction introduced by Eckart and later modified by
Yasumori and Fueki (mYF). The mVPT2, mYF and mSVPT4 theories have been
applied to various 1D model systems and the results are promising. The mVPT2 and
mYF theories have been successfully generalized to multidimensional systems and
applied to calculate thermal rates for the collinear H+HH and D+HH reactions.